US2481307A - Stabilization of halogen-containing plastic compositions - Google Patents

Stabilization of halogen-containing plastic compositions Download PDF

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Publication number
US2481307A
US2481307A US740974A US74097447A US2481307A US 2481307 A US2481307 A US 2481307A US 740974 A US740974 A US 740974A US 74097447 A US74097447 A US 74097447A US 2481307 A US2481307 A US 2481307A
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salicylate
isopropyl
heat
light
stabilizers
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Garner Philip James
Croft-White Peter Gordon
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Shell Development Co
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Shell Development Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B1/00—Film strip handling
    • G03B1/42—Guiding, framing, or constraining film in desired position relative to lens system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
    • C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring
    • C07C65/05—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring o-Hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
    • C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring
    • C07C65/05—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring o-Hydroxy carboxylic acids
    • C07C65/10—Salicylic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/138—Phenolates

Definitions

  • This invention relates to heat and light stabilized plastic compositions containing polymers which evolve hydrogen halide upon decomposition. More specifically, the invention relates to plastic compositions, containing polymers that normally become discolored and undergo a change of physical properties when exposed to natural or artificial light and heat in the ordinary course of their use, which have been heat and light stabilized by the addition of small amounts of certain metal salts of substituted salicylic acids. In one of its most specific embodiments the invention relates to heat and light stabilized vinyl resins, which contain polymers of halogenated vinyl compounds and small amounts of stabilizers consisting of oil soluble substituted salicylates oi metals which do not catalyze the evolution of hydrogen halide from the polymer.
  • a heat and light stabilized plastic composition refers to a composition containing an additive substance, the presence of which causes the composition to exhibit greater resistance to the changes in physical properties which are initiated by the effects of heat and/or light radiation than are characteristic of otherwise identical compositions which do not contain the additive substance.
  • Thermoplastic resins containing polymers formed by the polymerization of monomers in which aliphatic carbon atoms are attached to halogen atoms, particularly the resins oi the vinyl family, are considerably restricted in application because of their limited stability when subjected to the effects of light radiation, or to elevated temperatures. This instability is well known and has long been a problem in the art of manufacturing plastic compositions. Many careiiul investigations have been made of the causes and character of this commonly occurring failure, as, for example, the decomposition of compositions containing polyvinyl chloride. It has been found that in both the thermal and photochemical decomposition of polyvinyl chloride, the polymer becomes dark and eventually black while at the same time hydrogen chloride is liberated.
  • the decomposition appears to be autocatalytic, the presence 01' the evolved hydrogen chloride accelerating the reaction which further liberates hydrogen chloride. It has long been common practice to inhibit this decomposition reaction by the incorporation into the plastic composition of a "stabilizer" which will combine with the hydrogen chloride produced, or otherwise render it inoperative as a catalyst. Many them as stabilizers.
  • inorganic compounds as the alkali and alkaline earth metal carbonates. oxides, etc., antioxidantcompounds as the substituted phenols, napthols, etc., the alkali metal salts of fatty acids, aromatic amines as 1,4-diaminobenzene, and numerous other materials.
  • Inorganic materials particularly white lead or basic lead carbonate, impart considerable heat stability to vinyl resins and are commonly emplayed in this connection, but since the inorganic materials, as well as certain of the metal salts of fatty acids, are relatively insoluble in the plasticizers commonly employed, it is seldom possible to obtain transparent compositions containing
  • the various organic materials particularly nitrogenous compounds, impart light stability but, as in the case of 1,4-dl- ,aminobenzene in polyvinyl chloride many organic compounds are subject to forming cross-links between the polymer chalns with a resultant change in the physical properties of the polymer.
  • a composition which is both a heat and light stabilizer must exhibit a wide variety of relatively unrelated physical and chemical properties such as: compatibility with the polymer and plasticizer in the proportions required for eiiective stabilization, low volatility to such a degree that there is no loss of stabilizer either during the molding and/or curing processes or over the period of the useful life of the plastic composition, the property of combining with or otherwise preventing the liberated hydrogen halide from catalyzing further decomposition of the polymer without increasing the rate of evolution of the acid, etc.
  • many of the most important uses of the halogen-containing resins require special properties, such as transparency, which can only be obtained when the stabilizers employed are soluble in. as well as compatible with, the plasticizers used, or such as electrical insulating properties, which necessitate the incorporation or a stabilizing material which causes little or no deterioration of the properties of water adsorption,
  • volume resistivity, specific inductance capacity, power factor, etc., of the stabilized composition is the volume resistivity, specific inductance capacity, power factor, etc.
  • substituted salicylic acid salts of certain metals form oil soluble materials which are therefore soluble in a majority of the commonly employed plasticizers and which have the unobvious property of imparting heat and light stability to halogencontaining polymers without causing a loss in the transparency or electrical properties such as dielectric strength of the plastic composition. It has further been discovered that the salts formed by the partial or complete neutralization of substituted salicylic acids with metals which exhibit a minimum valence of two, when incorporated into plastic compositions, impart improved qualities of resistance to a thermoor photochemical decomposition accompanied by the evolution of a hydrogen halide.
  • the normal, basic or inner substituted salicylate salts exhibit many physical and chemical properties characteristic of the aromatic compounds and are thus soluble and/or compatible with an extremely wide range of polymeric materials and the commonly employed plasticizers.
  • These compounds may therefore be employed as stabilizers for a wide variety of halogen containing plastic compositions, being particularly suit able for compositions containing polymers or copolymers in which one or more components are formed from monomers as a vinyl halide, a halogenated vinyl type aromatic compound such as a styryl halide, in which the halogen atoms are preferably attached to the aliphatic portion of the compound, a vinylidene dihalide, a vinyl type ester of a halogen containing acid, a halogen containing vinyl alcohol ester of an organic acid, or the halogen containing polymers formed by the halogenation of the partially or completely polymerized material.
  • polymeric materials to which the invention is applicable include, polyvinyl chloride, polyvinyl bromide, interpolymers of vinyl chloride and vinyl acetate, chlorinated polyvinyl chloride chlorinated rubber, brominated rubber, chloroprene polymers and copolymers, chlorostyrene polymers and copolymers, fiuoroethylene polymers and copolymers, chloroacrylic acid ester polymers and copolymers, dichlorostyrene polymers and copolymers, and the like.
  • the present invention may therefore be generally stated as relating to plastic compositions containing polymers which are subject to decomposition and the evolution of hydrogen halide when exposed to the eflects of heat and/or light which have been heat and light stabilized by the incorporation into the composition of a small amount of a substituted salicylic acid salt of a metal having a minimum valence of two, and particularly to the saltsof metals having a minimum valence of two which form chelate rings, such as the metals of Group HA of the Periodic Table. While the formation of chelated rings as illustrated above is thought to impart the improved properties of solubility, compatibility etc., to the substituted salicylate stabilizers the invention is not limited to the formation of compounds of their particular structures.
  • a substance which is a suitable stabilizer for a plastic composition must possess a wide variety of physical and chemical properties which are not, in the ordinary chemical sense, closely related. While metal salts of weak organic acids are generally related more closely by the properties of the metal, it has been found that substituted salicylate salts of certain closely related metals may have widely divergent stabilizing properties. For example, while the substituted salicylate salts of the metals of Group 11A form particularly valuable stabilizers and plastic compositions containing them exhibit excellent heat and light stability in all of the measurable physical properties, the salts of a closely related element of Group IIB, zinc, im-
  • the particularly suitable heat and light stabilizers are the oil soluble, normal, basic or inner substituted salicylate salts of the elements of Group IIA of the Periodic Table, i. e., the alkaline earth metals, which are beryllium, magnesium, calcium, strontium, and barium; while suitable heat and, to varying extents, light stabilizers are formed by the substituted salicylate salts of metals with a minimum valence of two such as lead and nickel.
  • Substituted salicylic acids which are suitable to form the organic acid portion of the substituted salicylate salts are those in which the benzene nucleus, in addition to the carboxyl and hydroxyl groups in the 1 and 2 positions, contains at least one substituent group in the 3,4,5 or 6 position of the ring.
  • the substituent groups may consist of a plurality of attached groups or a single, group; in any case, the total number of carbon atoms contained in the substituent groups being between about 5 and 18 carbon atoms either in a single group or in a plurality of groups.
  • the substituent groups may be a plurality of low molecular weight alkyl radicals as, for example, ethyl, propyl, butyl, pentyl, etc., or any combination thereof with alkyl radicals of a higher molecular weight.
  • Unsaturated substituent groups have an added advantage of providing additional possible hydrogen halide removing reactions by the addition of the halogen acid to the unsaturated linkages as, for example, in attached vinyl, allyl, propenyl, butenyl, propynyl, butynyl, cyclopentenyl, butadienyl, cyclopentadienyl, cyclohexadienyl, etc., radicals.
  • Attached groups consisting of a plurality of branched chain alkyl or high molecular weight straight chain alkyls attached singly or in combination with other alkyl radicals are particularly suitable; for example, a plurality of radicals as isopropyl, isobutyl, isopentyl, 2,2-dimethyl pentenyl, isopropenyl, etc., or a single high molecular weight alkyl radical or a combination containing alkyl radicals as octyl, nonyl, octadecyl, lauryl, palmyl, stearyl, oleyl, etc.
  • Suitable substituent groups may consist of groups containing other atoms than only hydrogen and carbon as, for example, oxygen, and may be the only substituent group or may be attached to a salicylate nuclei containing other attached groups, examples of such non-hydrocarbyl substituent groups being ethoxyl, propoxyl, isopentoxyl, butoxyl, pentoxyl, isopropoxyl, isobutoxyl, acetoyl, pentinoyl, stearoyl, benzoyl, oleoyl, palmitoyl, pelargonoyl, propeolyl, propionyl, mor ptoluyl, vanilloyl, veratroyl, xyloyl, chaulmoogroyl, cinnamoyl, crotonyl, cumoyl, Z-furoyl, S-furoyl, hyd'rocaproyl, hydrocinnamoyl, etc.
  • substituted salicylate salts which have been found to be particularly effective heat and light stabilizers for resins of the vinyl family containing polymers and/or copolymers formed from halogenated vinyl monomers as, for example, from vinyl chloride, vinylidene chloride, vinyl bromide, chlorovinyl ethers;
  • esters and the like are the alkaline earth metal normal, basic and inner salts of stearoyl salicylic acid, octadecyl salicylic acid, octyl salicylic acid and di-isopropyl salicylic acid, such as beryllium stearoyl, octyl, octadecyl or di-isopropyl salicylate, magnesium stearoyl, octyl, octadecyl or di-isopropyl salicylate, calcium stearoyl, octyl, octadecyl or di-isopropyl salicylate, strontium stearoyl, octyl, octadecyl or di-isopropyl salicylate, cadmium stearoyl, octyl, octadecyl or diisopropyl salicylate, and barium
  • Illustrative examples of other substituted salicylate salts which are suitable heat and/or light stabilizers in accordance with the present invention are lithium stearoyl salicylate, lithium octodecyl salicylate, lithium octyl salicylate, lithium diisopropyl salicylate, nickel stearoyl salicylate, nickel di-isopropyl salicylate, nickel octyl salicylate, nickel octodecyl salicylate, lead di-lsopropyl salicylate, lead octyl salicylate,.lead octodecyl salicylate, lead stearoyl salicylate, magnesium dibutyl salicylate, magnesium di-isopentyl salicylate, calcium oleoyl salicylate, barium palmitoyl salicylate, calcium tri-isopropyl salicylate, calcium 3-propyl-5-isopropyl salicylate, .magnesium 3-ethy
  • the normal, basic and inner substituted salicylate salts of the present invention may be prepared by any of the well known methods of obtaining the metal salts of weak organic acids.
  • the following examples are given for the purpose of illustration and the scope of the present invention is in no way limited to the specific reactions and compounds illustrated below.
  • the oil-soluble stabilizers of the present invention are soluble in, or compatible with the plasticizer, stabilizers, fillers, waxes, color pigments and other additive agents commonly employed in the manufacture of vinyl resin compositions, and may therefore be used in conjunction with these additives to produce compositions for specialized uses.
  • the stabilizers of the present invention are effective when employed over a wide range of proportions, concentrations of from as little as 1% to as high as 10% or higher being suitable.
  • Particularly ,valuable stabilized vinyl resin compositions are those containing from about 5 to about 7 per cent ofsubstituted salicylic salt stabilizer in which the resulting compositions have been found to have properties of resistance to water adsorption, volume resistivity, specific conductance and power factor comparable with or 8 better than the unstabilized polymers in addition to greatlyimproved heat and light stability.
  • the stabilizers of the present invention may be incorporated into the plastic composition previous to or during the melting or may be predissolved in the plasticizer or added by any of the other methods commonly employed in the art.
  • the use of the stabilizers of the present invention greatly facilitates the preparation of transparent delicately dyed compositions which may be employed in the presence of light and elevated temperatures without alteration of the tint.
  • the oil-soluble substituted salicylates in addition to being soluble in many plasticizers may be incorporated over a wide range of proportions without adversely affecting the properties of water adsorption of the plastic composition.
  • many plastic compositions which could not be heat stabilized because they contained substances which would react with the commonly employed heat stabilizers, as the basic lead carbonates, etc., and consequently darken or change in color, can now be prepared with greatly improved qualities of heat and light stability.
  • Plastic compositions were prepared as in the preceding examples and molded into cylindrical discs which were maintained at a temperature of about 50 C. for 120 hours.
  • the initial and final volume resistivities of the various discs are recorded below with the ratio of the final volume resistivity to the initial volume resistivity.
  • the measurements were taken during each 24 hours of exposure and certain of the discs, for example, the composition containing basic lead carbonate, were found to vary considerably while those containing calcium and lead di-isopropyl salicylate and stearoyl salicylate, respectively, remained consistently high and those containing zinc octdecyl salicylate and 2,4dimethyl-6- tertiary-butyl phenol remained consistently low.
  • thedielectric constant and power ,factor at 800 capacitants were measured on the.
  • alicylat S octyl salicylate
  • ticular stabilizer material employed were placed in test tubes in which was suspended a small container of O. I. M. silver nitrate solution in such a manner that the lower portion of the tube containing the sample could be heated in a water bath while the upper portion containing the silver nitrate remained approximately at normal temperature.
  • the lower portion of the tubes was maintained at a temperature of 200 C. and the time of formation of a white precipitate of silver chloride recorded.
  • the following table illustrates the times in minutes required to cause the decomposition of the plastic compositions containing the various stabilizers under these conditions of extreme temperature which decomposed the unstabilized composition in only eight minutes.
  • EXAMPLE III The electrical properties of plasticized vinyl resin compositions containing various stabilizers.
  • a heat and light stabilized plastic composition containing polyvinyl chloride and between 1 and 10*, per cent by weight of normal barium octylsalicylate based on the weight of polyvinyl chloride.
  • Aheat and light stabilized plastic composition containing polyvinyl chloride and between 1 and 10 per cent by weight of basic lead octadecylsalicylate based on the weight of polyvinyl chloride.
  • a heat and light stabilized plastic composition containing polyvinyl chloride and an amount equal to between 1 and 10 per cent by weight based on the weight of polyvinyl chloride of the calcium inner salt of diisopropylsalicylic acid.
  • a heat and light stabilized plastic compominutes sition containing a polymeric vinyl halide and between 1 and 10 per cent by weight of an alka- Strontiumdi-isopropylialicylate 38 line earth metal inner salt of diisopropylsallfiiiitifiiififitifibtithes2m;ai ig W acid based on the ht of pvlyvieyl halide- Nickeldi-lsnpfopylSl11l0y 8 5.
  • a heat and light stabilized plastic composition containing at least one polymerized halogen containing vinyl compound and as a stabilizer an alkaline earth metal salt of a salicylic acid in which an alkyl radical containing from 8 to 18 carbon atoms is attached to the salicylate nucleus.
  • a heat and light. stabilized plastic composition containing at least one polymerized halogen containing vinyl compound and as a stabilizer an alkaline earth metal-salt of a salicylic acid in which alkyl radicals having a total of from 5 to 18 carbon atoms are attached to the salicylate nucleus.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US740974A 1946-05-02 1947-04-11 Stabilization of halogen-containing plastic compositions Expired - Lifetime US2481307A (en)

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GB13406/46A GB617620A (en) 1946-05-02 1946-05-02 Stabilised compositions containing polymers which evolve hydrogen chloride on decomposition

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE976091C (de) * 1954-07-28 1963-02-21 Argus Chem Stabilisierungsmittel fuer Polyvinylchlorid und Vinylchlorid-Mischpolymerisate
US3238163A (en) * 1961-06-30 1966-03-01 Ici Ltd Dye receptive polyolefin compositions comprising a magnesium or zinc compound and a hydroxy substituted benzophenone
US3274222A (en) * 1961-01-04 1966-09-20 Chem Fab Hoesch Kg Lead stabilizers for polyvinyl chloride and polyvinyl chloride copolymers
US3296192A (en) * 1961-12-28 1967-01-03 Hercules Inc Stabilization of polyolefins with nickel salts of aromatic compounds
FR2207904A1 (en)) * 1972-11-22 1974-06-21 Ciba Geigy Ag
FR2762839A1 (fr) * 1997-04-30 1998-11-06 Oreal Nouveaux derives de l'acide salicylique et leur utilisation dans une composition cosmetique et/ou dermatologique

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1037045B (de) * 1953-03-05 1958-08-21 Advance Produktion G M B H Deu Hitzehaertbares UEberzugsmittel auf Basis von Polysiloxanen

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2075543A (en) * 1934-07-10 1937-03-30 Union Carbide & Carbon Corp Stabilization of vinyl resins and compositions produced thereby
US2240764A (en) * 1939-03-01 1941-05-06 Dow Chemical Co Distillation of vinyl aromatic compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2075543A (en) * 1934-07-10 1937-03-30 Union Carbide & Carbon Corp Stabilization of vinyl resins and compositions produced thereby
US2240764A (en) * 1939-03-01 1941-05-06 Dow Chemical Co Distillation of vinyl aromatic compounds

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE976091C (de) * 1954-07-28 1963-02-21 Argus Chem Stabilisierungsmittel fuer Polyvinylchlorid und Vinylchlorid-Mischpolymerisate
US3274222A (en) * 1961-01-04 1966-09-20 Chem Fab Hoesch Kg Lead stabilizers for polyvinyl chloride and polyvinyl chloride copolymers
US3238163A (en) * 1961-06-30 1966-03-01 Ici Ltd Dye receptive polyolefin compositions comprising a magnesium or zinc compound and a hydroxy substituted benzophenone
US3296192A (en) * 1961-12-28 1967-01-03 Hercules Inc Stabilization of polyolefins with nickel salts of aromatic compounds
FR2207904A1 (en)) * 1972-11-22 1974-06-21 Ciba Geigy Ag
FR2762839A1 (fr) * 1997-04-30 1998-11-06 Oreal Nouveaux derives de l'acide salicylique et leur utilisation dans une composition cosmetique et/ou dermatologique
US5917088A (en) * 1997-04-30 1999-06-29 L'oreal Salicyclic acid derivatives, process of preparation and uses thereof

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GB617620A (en) 1949-02-09
NL64136C (en))
BE472943A (en))

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